DE2521649C2 - 3-Amino-4-carbalkoxybenzoic acid-4'-phenoxyanilide, process for their preparation and their use - Google Patents
3-Amino-4-carbalkoxybenzoic acid-4'-phenoxyanilide, process for their preparation and their useInfo
- Publication number
- DE2521649C2 DE2521649C2 DE2521649A DE2521649A DE2521649C2 DE 2521649 C2 DE2521649 C2 DE 2521649C2 DE 2521649 A DE2521649 A DE 2521649A DE 2521649 A DE2521649 A DE 2521649A DE 2521649 C2 DE2521649 C2 DE 2521649C2
- Authority
- DE
- Germany
- Prior art keywords
- parts
- volume
- amino
- acid
- nitro
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 238000002360 preparation method Methods 0.000 title claims description 5
- 238000000034 method Methods 0.000 title claims description 3
- 239000000460 chlorine Substances 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 125000001246 bromo group Chemical group Br* 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000006297 carbonyl amino group Chemical group [H]N([*:2])C([*:1])=O 0.000 claims 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 17
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 8
- -1 4-aminodiphenyl ethers Chemical class 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 150000001805 chlorine compounds Chemical class 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229960000583 acetic acid Drugs 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000012362 glacial acetic acid Substances 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 125000000449 nitro group Chemical class [O-][N+](*)=O 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 2
- WOYZXEVUWXQVNV-UHFFFAOYSA-N 4-phenoxyaniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC=C1 WOYZXEVUWXQVNV-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 125000004442 acylamino group Chemical group 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 150000002828 nitro derivatives Chemical class 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- LHJGJYXLEPZJPM-UHFFFAOYSA-N 2,4,5-trichlorophenol Chemical compound OC1=CC(Cl)=C(Cl)C=C1Cl LHJGJYXLEPZJPM-UHFFFAOYSA-N 0.000 description 1
- RANCECPPZPIPNO-UHFFFAOYSA-N 2,5-dichlorophenol Chemical compound OC1=CC(Cl)=CC=C1Cl RANCECPPZPIPNO-UHFFFAOYSA-N 0.000 description 1
- RWDOREOERSVIRK-UHFFFAOYSA-N 4-(2,4-dichlorophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=C(Cl)C=C1Cl RWDOREOERSVIRK-UHFFFAOYSA-N 0.000 description 1
- YTISFYMPVILQRL-UHFFFAOYSA-N 4-(4-chlorophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=C(Cl)C=C1 YTISFYMPVILQRL-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000003436 Schotten-Baumann reaction Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- WLJVXDMOQOGPHL-UHFFFAOYSA-N benzyl-alpha-carboxylic acid Natural products OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- ZWWCURLKEXEFQT-UHFFFAOYSA-N dinitrogen pentaoxide Chemical compound [O-][N+](=O)O[N+]([O-])=O ZWWCURLKEXEFQT-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QUMITRDILMWWBC-UHFFFAOYSA-N nitroterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C([N+]([O-])=O)=C1 QUMITRDILMWWBC-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 229960003424 phenylacetic acid Drugs 0.000 description 1
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000000284 resting effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 125000004436 sodium atom Chemical group 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- IUTCEZPPWBHGIX-UHFFFAOYSA-N tin(2+) Chemical class [Sn+2] IUTCEZPPWBHGIX-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/0003—Monoazo dyes prepared by diazotising and coupling from diazotized anilines
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/10—Monoazo dyes prepared by diazotising and coupling from coupling components containing hydroxy as the only directing group
- C09B29/18—Monoazo dyes prepared by diazotising and coupling from coupling components containing hydroxy as the only directing group ortho-Hydroxy carbonamides
- C09B29/20—Monoazo dyes prepared by diazotising and coupling from coupling components containing hydroxy as the only directing group ortho-Hydroxy carbonamides of the naphthalene series
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
COClCOCl
wobei R die in Anspruch 1 genannte Bedeutung hat und A eine in eine Aminogruppe überführbare Gruppe bedeutet, mit 4-Aminodiphenyläthern der allgemeinen Formelwhere R has the meaning given in claim 1 and A is a group which can be converted into an amino group means with 4-aminodiphenyl ethers of the general formula
H2NH 2 N
wobei X und η die in Anspruch 1 genannten Bedeutungen haben, kondensiert und bei den so erhaltenen Produkten die Gruppe A in die Aminogruppe überführt. 3. Verwendung der Verbindungen nach Anspruch 1 als Diazokomponente^where X and η have the meanings given in claim 1, condensed and, in the products thus obtained, the group A is converted into the amino group. 3. Use of the compounds according to claim 1 as a diazo component ^
Gegenstand der Erfindung sind 3-Amino-4-carbalkoxybenzoesäure-4'-phenoxyanilide der allgemeinen Formel 1The invention relates to 3-amino-4-carbalkoxybenzoic acid-4'-phenoxyanilides of the general formula 1
COORCOOR
0)0)
wobei R die Methyl- oder Ethylgruppe, X Wasserstoff- oder gleiche oder verschiedene Chlor oder Bromatome, und π eine ganze Zahl zwischen i und 4 bedeutet, sowie ein Verfahren zu ihrer Herstellung, bei der man 4-Carbalkoxybenzoylchloride der allgemeinen Formel Hwhere R is the methyl or ethyl group, X is hydrogen or identical or different chlorine or bromine atoms, and π is an integer between i and 4, as well as a process for their preparation, in which one 4-carbalkoxybenzoyl chlorides of the general formula H
COORCOOR
(H)(H)
COClCOCl
wobei R die vorstehend angegebene Bedeutung hat und A eine in eine Aminogruppe überführbare Gruppe, wie Nitro-oder Acylamino./.. B.eine Acctylaminogruppc bedeutet, mit 4-Aminodiphenyläthern der Formel IIIwhere R has the meaning given above and A is a group which can be converted into an amino group, such as Nitro or acylamino./ .. B. means an acctylamino group with 4-aminodiphenyl ethers of the formula III
H3NH 3 N
(ΠΙ)(ΠΙ)
wobei X und π die vorstehend genannten Bedeutungen haben, beispielsweise nach Schotten-Baumann, kondensiert und anschließend die Gruppe A in die Aminogruppc überführt, beispielsweise die Nitrogruppe reduziert bzw. die Acylaminogruppe hydrolysiert.where X and π have the meanings given above, for example according to Schotten-Baumann, condensed and then the group A is converted into the amino group, for example the nitro group is reduced or the acylamino group is hydrolyzed.
Die 4-Aminodiphenyläther der allgemeinen Formel III können beispielsweise durch Umsetzung der Alkaliphenolate der allgemeinen Formel IVThe 4-aminodiphenyl ethers of the general formula III can, for example, by reacting the alkali metal phenolates of the general formula IV
OMOM
wobei X und /? die vorstehend genannten Bedeutungen haben und Μ ein Kalium- oder Natriumatom bedeutet, mit p-Nitrochlorbenzol in Gegenwart von Phenol oder einem organischen Lösemittel, wie beispielsweise Dimethylformamid oder Dimethylsulfoxid, und anschließender Reduktion der Nitrogruppe hergestellt werden. Als 4-Aminodiphenyläther können beispielsweise eingesetzt werden:where X and /? have the meanings given above and Μ denotes a potassium or sodium atom, with p-nitrochlorobenzene in the presence of phenol or an organic solvent such as dimethylformamide or dimethyl sulfoxide, and subsequent reduction of the nitro group. as 4-aminodiphenyl ethers can be used, for example:
4-Aminodiphenylether, 4-Amino-4'-chlordiphenyläther, 4-Amino-2\4-aminodiphenyl ether, 4-amino-4'-chlorodiphenyl ether, 4-amino-2 \
S'-dichlordiphenyläther, 4-Amino-2',4'-dichlordiphenyläther, 4-Amino-2',5'-dichlordipheny!äther, 4-Amino-2',4'(5'-trichlordiphenyläther, 4-Amino-2'3\4',5'-tetrachlordiphenyläther, 4-Amino-2'-bromdiphenyläther, 4-Amino-4'-bromdiphenyläther.S'-dichlorodiphenyl ether, 4-amino-2 ', 4'-dichlorodiphenyl ether, 4-amino-2', 5'-dichlorodiphenyl ether, 4-amino-2 ', 4' ( 5'-trichlorodiphenyl ether, 4-amino- 2'3 \ 4 ', 5'-tetrachlorodiphenyl ether, 4-amino-2'-bromodiphenyl ether, 4-amino-4'-bromodiphenyl ether.
Die 4-Carbalkoxybenzoylchloride der allgemeinen Formel 11 lassen sich beispielsweise durch partielle Hydrolyse der Nitroterephtalsäuredialkylester und anschließende Umsetzung der erhaltenen 3-Nitro-4-carbalkoxybenzoesäuren mit den üblichen Reagenzien zur Herstellung von Säurechloriden, wie beispielsweise Thionylchlorid oder Phosphoroxytrichlorid, herstellen.The 4-carbalkoxybenzoyl chlorides of the general formula 11 can be obtained, for example, by partial hydrolysis the dialkyl nitroterephthalate and subsequent reaction of the 3-nitro-4-carbalkoxybenzoic acids obtained with the usual reagents for the preparation of acid chlorides, such as thionyl chloride or phosphorus oxytrichloride.
Analog dazu werden die S-Acylamino^-carboalkoxybenzoesäuren in die Säurechloride umgewandelt. Hierbei bedeuten die »Acyl«-Gruppe bevorzugt eine Benzoyl- oder Alkanoylgruppe mit 2 bis 5 Kohlenstoffatomen, insbesondere die Acetylgruppe.Analogously, the S-acylamino ^ -carboalkoxybenzoic acids are converted into the acid chlorides. Here the "acyl" group preferably means a benzoyl or alkanoyl group with 2 to 5 carbon atoms, especially the acetyl group.
Die nach der Kondensation der Säurechloride Il mit den Aminen der Formel III erhaltenen Verbindungen werden entweder durch Behandeln der N-Acylgruppe mit Säure oder Laugen oder durch Reduktion der Nitrogruppe, beispielsweise mit Metallen, wie Eisen oder Zink, oder Zinn(ll)salzen, vorzugsweise durch Hydrierung unter Druck in Gegenwart von Nickelkatalysatoren, in die entsprechenden S-Amino^-carbalkoxybenzoesäure-4'-phenoxyanilide überführt.The compounds obtained after the condensation of the acid chlorides II with the amines of the formula III are either by treating the N-acyl group with acid or alkali or by reducing the Nitro group, for example with metals such as iron or zinc, or tin (II) salts, preferably by hydrogenation under pressure in the presence of nickel catalysts, into the corresponding S-amino ^ -carbalkoxybenzoic acid-4'-phenoxyanilide convicted.
Die erfindungsgemäßen Verbindungen werden in guter Ausbeute und Reinheit erhalten. Sie lassen sich gegebenenfalls aus den verschiedensten Lösemitteln wie beispielsweise Alkoholen, Benzol, Toluol oder Eisessig Umkristallisieren.The compounds according to the invention are obtained in good yield and purity. You let yourself optionally from a wide variety of solvents such as alcohols, benzene, toluene or glacial acetic acid Recrystallize.
Die neuen S-Amino^-carbalkoxybenzoesäure^'-phenoxyanilide sind wertvolle Diazokomponenten. Insbesondere lassen sie sich in diazotierter Form beispielsweise mit 2-Hydroxy-3-naphthoesäureanilid-Derivaten zu Azopigmenten kuppeln, die sich durch klare Nuancen und sehr gute Echtheiten, wie Licht- und Migrationsechtheiten auszeichnen.The new S-amino ^ -carbalkoxybenzoic acid ^ '- phenoxyanilide are valuable diazo components. In particular they can be in diazotized form, for example with 2-hydroxy-3-naphthoic acid anilide derivatives Azo pigments couple, which are characterized by clear nuances and very good fastness properties, such as light and migration fastnesses distinguish.
Die folgenden Beispiele sollen die Herstellung der erfindungsgemäßen Verbindungen illustrieren. Teile und Prozente beziehen sich auf das Gewicht, sofern nichts anderes angegeben ist. Da:; Verhältnis von Gewichts- zu Volumenteilen ist das vom Kilogramm zum Liter.The following examples are intended to illustrate the preparation of the compounds according to the invention. Parts and Percentages are based on weight, unless otherwise stated. There:; Ratio of weight to Dividing by volume is that from the kilogram to the liter.
450 Teile S-Nitro^-carbomethoxybenzoesäure werden in 1000 Vol.-Teilen Chlorbcnzol gelöst. Durch azeotropes Abdestillieren von ca. 100 Vol.-Teilen Chlorbenzol wird der Ester wasserfrei gemacht. Unter Zusatz von 10 Vol.-Teilen Dimethylformamid, das vorher getrocknet wurde, läßt man tropfenweise bei 70cC 260Teile (= 158 Vol.-Teile) Thionylchlorid einlaufen. Nach 4—5 Stunden zieht man überschüssiges Thionylchlorid mit geringen Mengen an Chlorbenzol im Wasserstrahlvakuum ab. Das Säurechlorid wird, in Chlorbenzol gelöst, anteilmäßig zur Umsetzung gebracht.450 parts of S-nitro ^ -carbomethoxybenzoic acid are dissolved in 1000 parts by volume of chlorobenzene. The ester is rendered anhydrous by azeotropic distilling off of approx. 100 parts by volume of chlorobenzene. With addition of 10 parts by volume of dimethylformamide, which was previously dried, is allowed to run in dropwise at 70 c C 260Teile (= 158 parts by volume) of thionyl chloride. After 4-5 hours, excess thionyl chloride is drawn off with small amounts of chlorobenzene in a water-jet vacuum. The acid chloride, dissolved in chlorobenzene, is reacted proportionately.
374 Teile 4-Aminodiphenyläther werden bei 80°C in 500 Vol.-Teilen Chlorbcnzol und 160 Vol.-Teilen Pyridin gelöst. Dazu läßt man in 3 Stunden das in Chlorbenzol gelöste Säurcehlorid zulaufen. Es wird kurz auf 1000C geheizt. Der Ansatz wird dann auf 4000 Vol.-Teile 2%ige Natriumcarbonatlösung gegeben. Beim Erkalten fällt das Produkt aus. Mit Wasserdampf werden Chlorbenzol und Pyridin abgeblasen. Die Ausbeute beträgt nach Abnutschen und Trocknen 620 Teile der Verbindung der Formel:374 parts of 4-aminodiphenyl ether are dissolved in 500 parts by volume of chlorobenzene and 160 parts by volume of pyridine at 80.degree. To this end, the acid chloride dissolved in chlorobenzene is run in over the course of 3 hours. It is briefly heated to 100 0 C. The batch is then added to 4000 parts by volume of 2% strength sodium carbonate solution. The product precipitates when it cools down. Chlorobenzene and pyridine are blown off with steam. After suction filtration and drying, the yield is 620 parts of the compound of the formula:
1515th 2020th 2525th 3030th 3535 4040 4545
5050
6060
Smp. 146-148° C.M.p. 146-148 ° C.
256 Teile dieses 4-(3'Nitro-4'-carbomethoxybenzoylamino)-diphenyläthers werden in 1500 Vol.-Teilen Ethanol unter Zusatz von 15 Teilen Nickelkatalysalor auf Kieselgur bei 50"C und 50 bar in 3 Stunden reduziert Die heiße Lösung wird abgenutscht und im Filtrat das Amin durch Zugabe von Wasser vorsichtig gefällt. Es wird abgenutscht. Nach dem Trocknen kann das Produkt der Formel256 parts of this 4- (3'nitro-4'-carbomethoxybenzoylamino) diphenyl ether are dissolved in 1500 parts by volume of ethanol with the addition of 15 parts of nickel catalyst reduced to kieselguhr at 50 "C and 50 bar in 3 hours hot solution is suction filtered and the amine is carefully precipitated in the filtrate by adding water. It will sucked off. After drying, the product can use the formula
COOCH3 COOCH 3
NH2 NH 2
CONH-CONH-
aus Ethanol, Benzol oder Eisessig umkristallisiert werden: Ausbeute 70%, Smp. 172—175°C.recrystallized from ethanol, benzene or glacial acetic acid: yield 70%, melting point 172-175 ° C.
105 Teile 4-Amino-4'chlordiphenyläther werden in einem Gemiscii aus 100 Vol.-Teilen Toluol und 50 Vol.-Teilen Pyridin bei 70—800C gelöst. Unter Ruhten läßt man tropfenweise 122Teile S-Nitro^-carbomethoxybenzoylchlorid zutropfen. Nach ungefähr 4 Stunden ist die Reaktion beendet. Man gibt dann auf 2000 Vol.-Teile 2°/oige Natriumcarbonatlösung und destilliert das Toluol und Pyridin mit Wasserdampf ab. Ausbeute nach dem Trocknen: 190 Teile. Snip. 134° C.105 parts of 4-amino-4'chlordiphenyläther are parts by volume of pyridine dissolved in a Gemiscii 100 parts by volume of toluene and 50 at 70-80 0 C. While resting, 122 parts of S-nitro ^ -carbomethoxybenzoyl chloride are added dropwise. The reaction has ended after about 4 hours. 2% sodium carbonate solution is then added to 2000 parts by volume and the toluene and pyridine are distilled off with steam. Yield after drying: 190 parts. Snip. 134 ° C.
190 Teile dieses 4-(3"-Nitro-4"carbomethoxy-benzoylamino)-4'-chlordiphenyläthers werden in 2000 Vol.-Teilen Ethanol unter Zugabe von 12 g Nickelkatalysator (RCH 55/5; Ruhrchemie) und 20 g Natriumacetat bei 500C und 70 bar innerhalb von 3 Stunden reduziert.190 parts of this 4- (3 "-Nitro-4" carbomethoxy-benzoylamino) -4'-chlorodiphenyl ether are dissolved in 2000 parts by volume of ethanol with the addition of 12 g of nickel catalyst (RCH 55/5; Ruhrchemie) and 20 g of sodium acetate at 50 0 C and 70 bar reduced within 3 hours.
Nach Aufarbeitung, wie in Beispiel 1 beschrieben, erhält man 134 Teile der Verbindung der FormelAfter working up as described in Example 1, 134 parts of the compound of the formula are obtained
COOCH3 COOCH 3
Smp. 170-1751C.M.p. 170-175 1 C.
In 171 Teilen 2,5-Dichlorphenol werden von 75° —1200C ansteigend 67 Teile Kaliumhydroxid (86°/oig) nach und nach eingetragen. Man rührt 1—2 Stunden zur Vervollständigung der Reaktion nach. Man läßt dann bei 900C 157 Teile ( = 125 Vol.-Teile) 4-Chlornitrobenzol in 2 Stunden zutropfen, wobei die Temperatur bis 135°C steigen kann. Nach insgesamt 4 Stunden gießt man den Kolbeninhalt auf 500 Vol.-Teile 2%ige Natronlauge und rührt bei 900C I Stunde gut durch. Die wäßrige Oberschicht wird abgetrennt und mehrere Male mit Wasser gewaschen. Danach kühlt man aul 30—4O0C ab, wobei das Produkt granuliert und fest wird. Das Waschwasser wird auf pH 1 gestellt. Der ausgefallene 4-Nitro-2',5'-dichlorphenyläther wird abgenulscht und kann aus Äthanol umkristallisiert werden.(Smp. 96°C, Ausbeute 88%).In 171 parts of 2,5-dichlorophenol 67 parts of potassium hydroxide are (/ oig 86 °) was added gradually increasing from 75 ° -120 0 C. The mixture is stirred for 1-2 hours to complete the reaction. 157 parts is then allowed 4-chloronitrobenzene were added dropwise in 2 hours at 90 0 C (= 125 parts by volume), whereby the temperature may rise to 135 ° C. After a total of 4 hours, pour the contents of the flask to 500 parts by volume of 2% sodium hydroxide solution and stirred by well at 90 0 CI hour. The aqueous top layer is separated and washed several times with water. It is then cooled aul 30-4O 0 C., the product being granulated and solidified. The washing water is adjusted to pH 1. The precipitated 4-nitro-2 ', 5'-dichlorophenyl ether is washed off and can be recrystallized from ethanol (melting point 96 ° C., yield 88%).
In 400 Vol.-Teilen Eisessig werden 150 Teile Eisenfeilspäne eingetragen. Es wird auf 800C geheizt. Dann werden 152 Teile des 4-Nitro-2',5'-clieh!ordiphcnyläthcrs mich und nach eingetragen. Anschließend wird die Temperatur auf 105" — 110'1C gesteigert und die Reduktion durchgeführt.150 parts of iron filings are added to 400 parts by volume of glacial acetic acid. It is heated to 80 0 C. Then 152 parts of the 4-nitro-2 ', 5'-carbon dioxide are entered by me and by. Then the temperature to 105 "is - 110 '1 C increased and completed the reduction.
Nach 3 Stunden wird der Kolbcninluilt heiß abgenutscht. Zu dem Fihrat wird die gleiche Menge Wasser gegeben, wobei der Aminodiphenylether ausfüllt. Kr wird durch Abnutschen abgetrennt und getrocknet. (Smp. 72-74X).After 3 hours, the Kolbcninluilt is sucked off hot. The same amount of water is added to the fihrat given, where the aminodiphenyl ether fills. Kr is separated off by suction filtration and dried. (M.p. 72-74X).
In einem Gemisch uns 300 Vol.-Teilen Chlorbenzol und 30 Vol.-Teilen Pyridin werden 70 Teile 2',5'-Dichlor-4-aminodiphenyläthcr bei 80' C gelöst. Unter Rühren erfolgt tropfenweise Zugabe von 70 Teilen in ChlorbenzolIn a mixture of 300 parts by volume of chlorobenzene and 30 parts by volume of pyridine, 70 parts of 2 ', 5'-dichloro-4-aminodiphenylether are added dissolved at 80 ° C. 70 parts of chlorobenzene are added dropwise with stirring
gelöstem S-Nitro^-carbomethoxybenzoylchlorid.dissolved S-nitro ^ -carbomethoxybenzoyl chloride.
Nach ca. 4 Stunden ist die Kondensation beendet. Nach dem Abkühlen des Ansatzes auf ca. 90cC gibt man dann auf 1000 Vol.-Teile 3°/oige Natriumcarbonatlösung und destilliert das Chlorbenzol und Pyridin mit Wasserdampf ab.The condensation has ended after approx. 4 hours. After cooling the batch to about 90 c C were then added to 1000 parts by volume of 3 ° / o sodium carbonate solution and distilled chlorobenzene and pyridine with steam.
Ausbeute an Nitroverbindung nach dem Trocknen 76 Teile, Smp. 78 C. λYield of nitro compound after drying 76 parts, m.p. 78 C. λ
37 Teile dieses 4-(3"-Nitro-4"carbomcthoxy-bcn/.oylaiiiino)-2',5'-l)idilordiphcnyUiilicrs werden in 380 Vol.-Teilen Eisessig eingetragen. Es wird auf 80°C geheizt. 38 Teile Eisenfeilspäne werden im Laufe einer Stunde eingetragen. Die Temperatur steigt an und wird bei 105" — 110" 3 Stunden gehalten. Die Aufarbeitung erfolgt wie in Beispiel 2 angegeben.37 parts of this 4- (3 "-Nitro-4" carbomcthoxy-bcn / .oylaiiiino) -2 ', 5'-l) idilordiphcnyUiilicrs are in 380 parts by volume of glacial acetic acid entered. It is heated to 80 ° C. 38 parts of iron filings are made in the course of a Hour entered. The temperature rises and is held at 105 "-110" for 3 hours. The work-up takes place as indicated in Example 2.
Ausbeute 30 Teile in Verbindung der FormelYield 30 parts in compound of formula
1515th
ClCl
2020th
Cl Smp. 217° C. Cl m.p. 217 ° C.
B e i s ρ i e 1 4B e i s ρ i e 1 4
100 Teile 2,4,5-Trichlorphenol werden bei 800C geschmolzen. Unter Rühren werden 30 Teile Kaliumhydroxid in 2 Stunden bei 80°C—120°C eingetragen. 81 Teile (62,5 Vol.-Teile) 4-Chiornitrobenzol läßt man bei 90°C tropfenweise zulaufen, wobei die Temperatur zum Schluß der Zugabe auf 150°C erhöht wird. In 4—5 Stunden ist die Reaktion beendet.100 parts of 2,4,5-trichlorophenol are melted at 80 0 C. 30 parts of potassium hydroxide are introduced at 80.degree. C.-120.degree. C. in the course of 2 hours, with stirring. 81 parts (62.5 parts by volume) of 4-chloronitrobenzene are allowed to run in dropwise at 90.degree. C., the temperature being increased to 150.degree. C. at the end of the addition. The reaction is over in 4-5 hours.
Nach dem Abkühlen auf 90°C gießt man den Kolbeninhalt unter Rühren auf 500 Vol.-Teile 3%ige Natronlauge. Die obere wäßrige Schicht wird abgetrennL Es wird mehrere Male bis zur Neutralität mit Wasser ausgerührt. Bei weiterem Abkühlen auf 30—5O0C granuliert das Produkt. Nach dem Ansäuern auf pH 1 wird abgesaugt. Eine weitere Reinigung kann durch Vakuumdestillation erfolgen. Der so erhaltene Nitroäther zeigt, aus Ethanol umkristallisiert, den Smp. 103— 105°C; die Ausbeute beträgt 120 Teile.After cooling to 90 ° C., the contents of the flask are poured into 500 parts by volume of 3% sodium hydroxide solution while stirring. The upper aqueous layer is separated off. It is stirred several times with water until neutral. On further cooling to 30-5O 0 C the product granulates. After acidification to pH 1, it is suctioned off. Further purification can be carried out by vacuum distillation. The nitro ether obtained in this way, recrystallized from ethanol, has a melting point of 103-105 ° C .; the yield is 120 parts.
140 Teile 2',4',5'-Trichlor-4-nitrodiphenyläther werden in 800 Vol.-Teile Ethanol eingerührt. Nachdem das Ganze auf 50°C geheizt worden ist, werden 330 Teile Eisenfeilspäne eingetragen, dazu dann 78 Vol.-Teile cone. Salzsäure zugesetzt In 5 Stunden wird die Reduktion durchgeführt. Dann wird mit 32%igem wäßrigem Ammoniak neutralisiert, erneut 1200 Vol.-Teile Äthanol zugesetzt und im Vakuum bis zur beginnenden Kristallisation eingeengt Die Kristallsuspension wird darauf in 2000 Vol.-Teile verd. Salzsäure bis zur stark sauren Reaktion (pH 1—2) eingerührt. Es wird abgesaugt und das Filtrat alkalisch gestellt, wobei das Amin ausfällt. Nach Abkühlen auf 0—100C wird abgesaugt und getrocknet, dann aus Benzol umkristallisiert. Der so erhaltene 2',4',5'-Trichlor-4-aminodiphenyläther hat den Smp. 168°C.140 parts of 2 ', 4', 5'-trichloro-4-nitrodiphenyl ether are stirred into 800 parts by volume of ethanol. After the whole thing has been heated to 50 ° C, 330 parts of iron filings are added, then 78 parts by volume of cone. Hydrochloric acid added. The reduction is carried out in 5 hours. Then it is neutralized with 32% aqueous ammonia, another 1200 parts by volume of ethanol are added and the mixture is concentrated in vacuo until crystallization begins. stirred in. It is filtered off with suction and the filtrate is made alkaline, the amine precipitating out. After cooling to 0-10 0 C is suction filtered and dried, then recrystallized from benzene. The 2 ', 4', 5'-trichloro-4-aminodiphenyl ether obtained in this way has a melting point of 168.degree.
In einem Gemisch aus 200 Vol.-Teilen Chlorbenzol und 20 Vol.-Teilen Pyridin werden 28 Teile 2',4',5'-Trichlor-4-aminodiphenyläther bei 8O0C gelöst. Unter Rühren erfolgt die tropfenweise Zugabe von 24 Teilen in Chlorbenzol gelöstem S-Nitro^-carbomethoxybenzoylchlorid.In a mixture of 200 parts by volume of chlorobenzene and 20 parts by volume of pyridine, 28 parts of 2 ', 4', 5'-trichloro-4-aminodiphenyläther dissolved at 8O 0 C. While stirring, 24 parts of S-nitro ^ -carbomethoxybenzoyl chloride dissolved in chlorobenzene are added dropwise.
Nach 4—5 Stunden ist die Reaktion beendet. Bei 90°C gibt man den Ansatz auf 1000 Vol.-Teile 2%ige Natriumcarbonatlösung und destilliert das Chlorbenzol und Pyridin mit Wasserdampf ab.The reaction is over after 4-5 hours. At 90 ° C., the batch is added to 1000 parts by volume of 2% strength Sodium carbonate solution and the chlorobenzene and pyridine are distilled off with steam.
Ausbeute an Nitroverbindung nach dem Trocknen: 34 Teile.Yield of nitro compound after drying: 34 parts.
In 300 VoL-Teile konz. Salzsäure werden nach und nach 100 Teile Zinn-lI-Chlorid (mit 2 Mol Wasser) unter gleichzeitigem Heizen bei 1000C eingetragen und gelöst. Zu der Lösung werden 38 Teile 4-(3"-Nitro-4"-carbomethoxy-benzoylamino)-2',4',5'-trichlordiphenyläther, die in 200 Vol.-Teilen Ethanol gelöst sind, hinzugegeben. Nach weiteren 2 Stunden wird abgekühlt und abgenutscht. Der Rückstand wird in 1000 Vol.-Teile 6%ige Kalilauge eingerührt Es wird erneut abgenutscht und neutral gewaschen. Das Amin der FormelConcentrated in 300 VoL parts. Hydrochloric acid are gradually added to 100 parts of tin-III chloride (with 2 mol of water) with simultaneous heating at 100 ° C. and dissolved. 38 parts of 4- (3 "-nitro-4" -carbomethoxy-benzoylamino) -2 ', 4', 5'-trichlorodiphenyl ether, which are dissolved in 200 parts by volume of ethanol, are added to the solution. After a further 2 hours, the mixture is cooled and suction filtered. The residue is stirred into 1000 parts by volume of 6% strength potassium hydroxide solution. It is suction filtered again and washed until neutral. The amine of the formula
5555
COOCH3 COOCH 3
6060
zeigt, aus Chlorbenzol umkristallisiert den Smp. 198—2000C Folgende weitere Verbindungen lassen sich entsprechend den Angaben in Beispiel 1 bis 4 herstellen: shows from chlorobenzene recrystallizing the mp 198-200 0 C. The following additional compounds can be prepared to 4 as detailed in Example. 1:
1010
2020th
ΧιΧι
2525th 3030th
4040
5050
5555
6060
Claims (2)
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2521649A DE2521649C2 (en) | 1975-05-15 | 1975-05-15 | 3-Amino-4-carbalkoxybenzoic acid-4'-phenoxyanilide, process for their preparation and their use |
| CH595076A CH620197A5 (en) | 1975-05-15 | 1976-05-12 | |
| US05/686,008 US4056553A (en) | 1975-05-15 | 1976-05-13 | 3-Amino-4-carboalkoxy-benzoic acid 4'-phenoxy-anilides |
| IT23228/76A IT1060568B (en) | 1975-05-15 | 1976-05-13 | 3 AMINO 4 CARBALCOSSIBENZO 4 PHENOS SIANYLIDES PROCESS FOR THEIR PREPARATION AND USE |
| BR7603068A BR7603068A (en) | 1975-05-15 | 1976-05-14 | 4'-3-AMINO-4-CARBALCOXYBENZOIC ACID PHENOXYNYLIDES, PROCESS FOR THEIR PREPARATION AND USE |
| JP51054465A JPS5929070B2 (en) | 1975-05-15 | 1976-05-14 | 3-Amino-4-carbalkoxybenzoic acid-4'-phenoxyanilide and its production and use method |
| CA252,622A CA1068719A (en) | 1975-05-15 | 1976-05-14 | 3-amino-4-carboalkoxy-benzoic acid 4'-phenoxy-anilides, process for their preparation and their use |
| GB19940/76A GB1527047A (en) | 1975-05-15 | 1976-05-14 | 3-amino-4-carboalkoxy-benzoic acid 4'-phenoxyanilides process for their preparation and their use |
| FR7614763A FR2310999A1 (en) | 1975-05-15 | 1976-05-17 | AMINO-BENZOIC ACID ANILIDES FOR USE AS DIAZOTATION COMPONENTS |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2521649A DE2521649C2 (en) | 1975-05-15 | 1975-05-15 | 3-Amino-4-carbalkoxybenzoic acid-4'-phenoxyanilide, process for their preparation and their use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| DE2521649A1 DE2521649A1 (en) | 1976-11-25 |
| DE2521649C2 true DE2521649C2 (en) | 1984-06-20 |
Family
ID=5946645
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE2521649A Expired DE2521649C2 (en) | 1975-05-15 | 1975-05-15 | 3-Amino-4-carbalkoxybenzoic acid-4'-phenoxyanilide, process for their preparation and their use |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US4056553A (en) |
| JP (1) | JPS5929070B2 (en) |
| BR (1) | BR7603068A (en) |
| CA (1) | CA1068719A (en) |
| CH (1) | CH620197A5 (en) |
| DE (1) | DE2521649C2 (en) |
| FR (1) | FR2310999A1 (en) |
| GB (1) | GB1527047A (en) |
| IT (1) | IT1060568B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6133685U (en) * | 1984-07-31 | 1986-02-28 | 日立プラント建設株式会社 | Printed circuit board draining device |
| BRPI0808786A2 (en) * | 2007-03-12 | 2014-09-16 | Bayer Cropscience Ag | DI-HALOGENOPHENOXYPHYMYLAMIDINES AND ITS USE AS FUNGICIDES |
| EP1969933A1 (en) * | 2007-03-12 | 2008-09-17 | Bayer CropScience AG | Di-halogen phenoxy phenylamidines and their use as fungicides |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2808433A (en) * | 1953-08-21 | 1957-10-01 | Du Pont | Benzene dicarboxylic acid derivatives |
| DE1644191C3 (en) * | 1961-12-29 | 1974-09-05 | Farbwerke Hoechst Ag, Vormals Meister Lucius & Bruening, 6000 Frankfurt | Water-insoluble monoazo dyes, process for their preparation and their use. Eliminated from: 1263202 |
| IT978318B (en) * | 1972-01-22 | 1974-09-20 | Hoechst Ag | N AMINOBENZOYL AMINOARYL SULPHONIC ACIDS AND PROCEDURE FOR THEIR PREPARATION |
-
1975
- 1975-05-15 DE DE2521649A patent/DE2521649C2/en not_active Expired
-
1976
- 1976-05-12 CH CH595076A patent/CH620197A5/de not_active IP Right Cessation
- 1976-05-13 IT IT23228/76A patent/IT1060568B/en active
- 1976-05-13 US US05/686,008 patent/US4056553A/en not_active Expired - Lifetime
- 1976-05-14 GB GB19940/76A patent/GB1527047A/en not_active Expired
- 1976-05-14 CA CA252,622A patent/CA1068719A/en not_active Expired
- 1976-05-14 BR BR7603068A patent/BR7603068A/en unknown
- 1976-05-14 JP JP51054465A patent/JPS5929070B2/en not_active Expired
- 1976-05-17 FR FR7614763A patent/FR2310999A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| CH620197A5 (en) | 1980-11-14 |
| US4056553A (en) | 1977-11-01 |
| FR2310999A1 (en) | 1976-12-10 |
| FR2310999B1 (en) | 1979-06-22 |
| GB1527047A (en) | 1978-10-04 |
| JPS5929070B2 (en) | 1984-07-18 |
| CA1068719A (en) | 1979-12-25 |
| DE2521649A1 (en) | 1976-11-25 |
| BR7603068A (en) | 1977-05-24 |
| JPS51143641A (en) | 1976-12-10 |
| IT1060568B (en) | 1982-08-20 |
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